Asphalt compositions



Patented Aug. 21, 1956 ASPHALT COIVIPOSITIONS Lowell T. Crews, Homewood, and Mathew L. Kalinowski,

Chicago, Ill., assignors to Standard Oil Company, Chicago, 111., a corporation of Indiana No Drawing. Application June 28, 1952, Serial No. 296,253

12 Claims. (Cl. 106-273) The present invention is directed to improvements in bitumen compositions, and particularly to improvements in mineral aggregate coating compositions, and more particularly relates to bitumen compositions having improved adherence to damp or wet mineral aggregates.

Residual oils and/or bituminous materials used in the preparation of pavements and roads do not coat and adhere well to mineral aggregates unless the aggregate is substantially dry, and for this reason, in conventional pavements or road construction practice, it is customary to dry the mineral aggregate by suitable well-known methods. Furthermore, water entering the road or pavement during service may have a detrimental effect in that it may displace the oil or bitumen from the surface of the aggre gate and thus diminish the bonding efiect of the oil and/ or bitumen. This materially shortens the life of the road or pavement requiring frequent repairs and is, therefore, uneconomical.

Mineral aggregates employed in road or pavement construction range in character from hydrophilic to hydrophobic. In general, siliceous and acidic minerals, such as sands .and gravels, tend to by hydrophobic while calcareous alkaline minerals, such as limestone, tend to be hydroph-ilic. It has been observed that the mineral aggregates appear to have a greater attraction for water than for oil or bitumens and that it is difficult to obtain, by conventional methods, complete or satisfactory coating of aggregates by oil or bitumen when water is present. Furthermore, even though satisfactory coating is obtained by using dry aggregate, the oil or bitumen tends to be displaced if water enters the pavement or road.

It is known that the coating of damp or wet mineral aggregates by oil or bitumen may be effected and the resistance 'of the coating to displacement or stripping by water may be improved by treating the aggregate with small amounts of water-soluble soap of a fatty acid in conjunction with water-soluble salt of a polyvalent heavy metal or activator. For optimum results with these reagents the relative amounts of the tworeagents must be carefully adjusted. Thus, when a divalent heavy metal is used as an activator, the amount of soap used should be substantially one mole per mole of activator; with a trivalent metal, between one and two moles of soap per mole of activator. Use of larger amounts of soap than this diminishes the effect obtained and this diminution of eifect increases with excess of soap over the proportions given when the amount of soap becomes equivalent to the activator, i. e., two moles of soap per mole of divalent metal or three per mole of trivalent metal, the beneficial effect of the reagent substantially disappears.

The above method has the disadvantage that the relative amounts of soap and polyvalent metal activator are critical and must be carefully adjusted for optimum results. Use of an excess of soap over the optimum amount diminishes rather than enhances the eflect obtained; the use of excess heavy metal to avoid the danger of excess soap is not harmful but increases the cost. Furthermore, the two reagents must be weighed or measured out and added to each batch as neither is soluble in the oil or bitumen; while this disadvantage may be partially overcome under favorable conditions by using in place of the soap, 3. fatty acid dissolved in the oil or bitumen, this expedient is very effective only under favorable conditions of low moisture content of the aggregate, adequate and efiicient mixing, etc. Under the conditions which are not at all severe, such as appreciable amounts of water and/or facilities for only moderately efficient mixing,

fatty acids appear not to be suificien'tly soluble in water to reach and react with the heavy metal ion to the required extent, and if added directly to the mixture or dissolved in the oil or bitumen are practically without effect.

Another important disadvantage of the above method is that a heavy polyvalent metal salt must be used with the soap. Furthermore, it has been found that while some limestones appear capable of adsorbing or reacting with polyvalent heavy metal ions and accordingly respond to some degree to the above method, a great many others do not, and with these it is difiicult or impossible to obtain a good coating by the above method. Also, since the foregoing method is not in general satisfactory with limestone, a great many natural mixed aggregates such as gravels containing both siliceous and calcareous particles will have only a portion of the particles coated.

In addition to the use of polyvalent fatty acid soaps in bitumens as mineral aggregate coating agents, certain organic nitrogen compounds, such as those obtained by reacting a polyamine with a fatty acid under conditions to form essentially amides, have been used for this purpose. However, although the .amide type asphalt additive are effective coating agents for acidic mineral aggregates, such as sands and gravels, they are ineffective on alkaline mineral aggregates, such as limestone.

It is an object of the present invention to provide a bituminous material having improved coating properties. It is also an object of the present invention to provide an oil or bitumen composition which will adhere to wetted acidic and alkaline mineral aggregates. Another object of the present invention is to provide a coating composition for acidic and alkaline mineral aggregates which will not be stripped therefrom by aqueous liquids. A further object is to provide a bitumen composition which will adhere to wette'd acidic mineral aggregates. Still another object is to provide a bitumen composition which will elfectively coat wetted alkaline mineral aggregates. Still another object of the invention is to provide a coating composition for acidic and alkaline mineral aggregates which can be applied without the necessity of drying the mineral aggregates and which will adhere there'to even in a wet condition. Another object of the invention is to provide a method of preventing stripping of the coating composition from acidic and alkaline miner-a1 aggregates by water after the road 'and/ or pavement is constructed. A further object of the invention is to provide a method of promoting the adherence of oil bituminous materials to siliceous and limestone aggregates without the necessi'ty of drying .the same. Other objects and advantages 'of the invention will become apparent as the following description thereof proceeds.

In accordance with the present invention, bitumens such as for example, road oils and asphalts having improved mineral aggregate coating properties, especially with respect to wet acidic and alkaline mineral aggregates, are obtained by incorporating in the bitumens from about 0.25% to about 5%, and preferably from about 0.5% to about 3%, by volume, of the oil-soluble produce obtained by reacting, under conditions to avoid amidation, an amine 'with a high molecular weight carboxylic acid mixture referred to hereinafter as acid mixture and hereinafter more fully described, Since amidation of amine soaps is brought about by the loss of Water at high temperatures, the reaction of the amine With the aforementioned acid mixture is carried out at temperatures below about 265 F, preferably below about 240 F., and more preferably at temperatures of from about 180 F. to about 225 F. to obtain a product essentially free of amido groups.

The high molecular weight carboxylic acid mixture reacted with the amine is obtained as a residue in the manufacture of sebacic acid by treatment of a member of the group consisting of ricinoleic acid and esters and salts of riconoleic acid with an alkali such as caustic soda. This acid residue, which is substantially non-volatile, being capable of only partial distillation even when molecular distillation procedures are employed, comprises essentially a mixture of long chain polyhasic carboxylic acids having a molecular weight in the range of from about 300 to about 1300, with an average molecular weight of about 1000, and characterized by an acid number of about 140165 and an iodine number of about 35-60. A method of preparing sebacic acid from which the non-volatile high molecular weight acid mixture is obtained is described in U. S. 2,182,056 issued to Bruson et al. December 5, 1939. The acid mixture as such may be used or we may use a purified acid mixture of the type described in U. S. 2,470,849 issued to W. E. Hanson May 24, 1949.

A suitable non-volatile high molecular weight acid mixture is the product marketed as VR-l Acid by Rohm and Haas Company. This product is a mixture of polybasic acids with an average molecular weight of about 1000, and with an average of slightly less than two carboxylic acid groups per molecule. A typical VR-l Aci sample has the following specification:

Acid number 150 Iodine number 36 Saponification number 172 Unsaponifiable matter percent 3.6 Moisture percent 0.86

As more fully described hereinafter, the above described high molecular weight acid mixture, per so, can be effectively employed in bitumen compositions to coat alkaline mineral aggregates.

The amine reactant employed in preparing the additive of the present invention can be an aliphatic amine, an aliphatic polyamine, or an aromatic polyamine. Particularly suitable aliphatic polyamines are alkylene polyamines containing at least two primary amino nitrogen atoms. Examples of alkylene poiyarnines suitable for the hereindescribed purpose are ethylene diamine, propylene diamine, diethylene-triamiue, diamylene triamine, triethylene tetramine, tripropylene tetramine, diethylenepropylene tetramine, tetraethylene pentamine, tetrabutylene pentamine, diethylendipropylene, pentarnine, butylene diamine, dihexylene triamine, and the like, or mixtures thereof. For example, a suitable polyamine product is a crude diethylene triamine containing minor amounts of ethylene diamine and triethylene tetramine. Other suitable aliphatic polyamines include those having the general formula RNH(CH2)3NH2, in which R is preferably a C to C18 aliphatic chain, and which are obtained by condensing the suitable amine with acrylonitrile and hydrogenating to the corresponding diamine. Commercially available aliphatic polyamines of this type are those marketed by Armour and Company as Duomeens, which are prepared by the condensation of a dodecyl (Coco) amine or an octadecyl (taiiow) amine with acrylonitrile followed by hydrogenation to the corresponding diamine product; these products are marketed as Duomeen C and Duomeen T, respectively. We may also employ aromatic polyamines, such as for example, phenylenediamine, and aliphatic amines, preferably those containing at least 8 carbon atoms in the alkyl group.

The amines may be chemically pure products or of a commercial quality. We have found as a desirable allphatic amine, the amine residue obtained in the following process. Fatty acids, derived from natural fatty acid glycerides, are converted into nitriles and the nitriles are reduced, principally, to primary amines, at temperatures below C. and under alkaline conditions. The reaction mass is then distilled, leaving a residue comprising essentially 10-25% primary amines and 3060% secondary amines. Depending upon the fatty acid employed, the aliphatic amines usually contain from about 8 to about 18 carbon atoms. Suitable amine residues are the products manufactured according to this general procedure and sold by Armour and Company under the tradename, Armeen Residues. These residues are obtained as distillation residues in the manufacture of products sold by Armour and Company under the tradenames Armeen CD. Armeen SD, Armen 8D, Armeen 12D, Arme-en 18D, etc. Armeen CD and Armeen SD are mixtures of primary amines prepared from coconut oil and soy bean oil, respectively, and other Armeens are mixtures of primary amines containing predominantly the number of carbon atoms specified in the tradename. We have found that bitumen compositions containing the Armeen Residues, per se, can be employed to effectively coat wetted acidic mineral aggregates.

In the preparation of the acid mixture and amine reaction product, it is preferable, although not essential, that the acid mixture be first dehydrated to obtain an essentially water-free product, or a product having not more than about 0.5% water. This can be readily accomplished by diluting the acid mixture with from about 10% to about 50% of a suitable hydrocarbon solvent, preferably a solvent rich in aromatic hydrocarbons, and by heating the diluted mixture at a temperature of about 210 F. to 290 F., while stirring and/or blowing with air orother suitable gaseous medium until the water content has been reduced to the desired value. If the acid mixture contains an undesirable amount of contaminants, they can be removed by permitting the hot solution to settle and decanting the diluted solution of purified mixture. If desired, the diluent may be removed from the dehydrated acid mixture by suitable means, such as by distillation under vacuum; however, we prefer to react the diluted acid mixture with the polyamine. The amine residues may be treated similarly.

Aromatic-rich hydrocarbon solvents suitable for this purpose are preferably those having boiling points above about 220 F. at atmospheric pressure and includes mononuclear aromatic hydrocarbons or condensed ring aromatics such as naphthalenes and mixtures of the higher boiling mono-nuclear aromatic hydrocarbons and polynuclear aromatic hydrocarbons.

A preferred source of mixed aromatic hydrocarbons suitable for this purpose is a light catalytic cycle stock obtained from a powdered or a fluid-type catalytic-type hydrocarbon cracking operation, in which gas oil or heavier hydrocarbons are cracked at a temperature of 800 F. to 1050 F., under a pressure of about atmos phere to 50 pounds per square inch, in the presence of suitable fluid or powdered catalyst, such as for example, silica-alumina, silica-magnesia, and other Well-known cracking catalysts. A method of conducting a fluidized cracking operation is described in U. 3.. 2,341,193 issued to Fred W. Scheincman February 8, 1944. Fractions from the process heavier than gasoline, depending upon their boiling range, are commonly referred to as light catalytic cycle stock, heavy catalytic cycle stock, and catalytic recycle residuum, which usually are cycled to cracking. A light catalytic cycle stock particularly well suited as a diluent for the dehydration of the acid mixture or the amine residue is a fraction having an aromatic content of at least about 40% and a distillation range between about 425 F. and about 560 F. A typical analysis of a suitable light catalytic cycle stock shows the material to be composed substantially of about 10% normal C12 to C20 parafiins, about 45% of other parafifins and naphthenes, about mono-nuclear aromatics which are mainly monoto hexa-alkylated benzenes, and about 40% polynuclear aromatics which are mainly alkyl naphthalenes, largely methylated naphthalenes. While we prefer to use a light catalytic cycle stock of the type described, hydrocarbon fractions from other catalytic conversion processes or thermal hydrocarbon conversion processes are suitable, provided they have an aromatic content of at least and a distillation range above about 220 F.

The acid mixture, preferably but not necessarily in solution in the light catalytic cycle stock or other suitable diluent, is reacted with the amine in the chemically equivalent ratio of from about 1:05 to about 1:2.0, and preferably in a ratio of about 1:1.2. The reaction is carried out at a temperature below about 265 F., and preferably of from about 180 F. to about 225 F. for not more than about one hour, preferably one-half hour. The temperature is then reduced as rapidly as possible to about 170 F., or lower. If the reaction is conducted in the manner described herein and the finished product is maintained until ready for use at a temperature below about 150 F., and preferably below about 140 R, an ellicient stable coating agent essentially free of amido groups is obtained.

While all acid mixture-amine reaction products prepared in the manner herein described are effective asphalt 1 additives, it is not to be implied that all are equivalents, since the specific activity of the described reaction products varies to some extent. polyamine reaction products are more elfective than the acid mixture mono-amine reaction products.

The preparation of amine acid mixture reaction products is illustrated by the following examples:

EXAMPLE I 39 parts of acid mixture (marketed by Rohm and Haas as VR-l Acid and having an equivalent weight of 386), 5 parts of 66% ethylenediamine, and 44 parts of light cycle stock, were mixed and heated for one hour at a temperature of about 240 F.

EXAMPLE II 39 parts of VR-l acid, 6 parts of 65% triethyleue tetramine and 45 parts light catalytic cycle stock were mixed and heated at 240 F. for one hour.

EXAMPLE III 39 parts of VR-l acid, and 17 parts of Duomeen C were mixed and heated for ten minutes at a temperature of 175 F.

EXAMPLE IV 39 parts of VR1 acid, 8 /2 parts of para phenylenediamine and 50 parts of light catalytic cycle stock were mixed and heated for one hour at 240 F.

EXAMPLE V 9.1 parts of VR-l acid, 21.4 parts of Armeen residues and 30.5 parts of light catalytic cycle stock were mixed and heated at a temperature of 210 F. to 240 F. for thirty minutes.

. EXAMPLE VI 18.2 parts of VR-l acid, 21.4 parts of Armeen residues, and 39.6 parts of light catalytic cycle stock were treated as in Example V.

The asphalt component of the herein-described composition may be of any bitumen which is useful for the coating of mineral aggregates used in the making of roads, highways, etc., or for the coating of other materials or surfaces where a water-resistant bond between the surface and the asphalt is advantageous or necessary. The term asphalt as employed herein is intended to be synonymous with bitumen and to cover a liquid, semisolid-or solid plastic bituminous material of the type employed in making or surfacing of highways and/or In general, the acid mixture- 6 pavements, caulking agents, sealing compounds, w'ater impervious paints, roofing materials, etc. Such asphalts or bituminous materials are mixtures of hydrocarbons of natural or pyrogenous origin, and are usually derived from petroleum or coal but may occur as such in nature. Asphalts may be derived as distillation resids or cracking resids with or without oxidation by air-blowing or by catalytic oxidation. The specific example of an asphalt of the type usually employed in the preparation of highways, etc. is a petroleum residuum cutback, fiuxed with.

to 700 F. to give a cutback product of the following specifications:

a light aromatic diluent boiling in the range of 400 F Cutback asphalt 1 Not less than. 2 Not more than.

Normally solid paving asphalts of the 40-200 penetration grades commonly used in road building fall within the following specifications:

Penetration at 77 F 40200. A. S. T. M. ductility at 77 F Not less than 200. Oliensis spot test Negative. Solubility in CCl4, percent Not less than 99.5. Specific gravity at 60 F Not less than Flash F. (C. O. C.) Not less than 475. Loss on heating 50 grams for 5 hours at 325 F., percent Not more than 0.5.

Penetration of residue at 77 F., 7

percent of original penetration Not less than 70-75.

The effectiveness of the herein-described acid mixture amine reaction products in enhancing the adhesion of asphalts to Wet mineral aggregates is determined by subjecting blends of asphalts and the described reaction products to one or more of the following tests:

A. lld'odified Colorado coating tests 20 grams of Ottawa sand or 20 grams of a 20 to 35 mesh limestone are weighed into a 2 oz. container and covered with one-half inch distilled water. One gram of the additive-containing asphalt is fioated on the water, the mixture then shaken for thirty seconds, and the extend of coating is determined by visual inspection; the results are expressed as Percent coated.

B. Wyoming stripping test Approximately 25 g. of Lander chips, all passing the -24; inch sieve and retained on the No. 4 sieve, is mixed by hand with 1.0 g. of fortified asphalt until the best possible coating is obtained. The mix is placed in an oven at 140 F. for 18 to 24 hours after which it is thoroughly remixed and is allowed to cool to room temperature. The sample is then immersed in distilled water at a temperature of 120 F., and is maintained at this temperature for a period of 24 hours. At the end of this period the area of the aggregate remaining coated is determined visually While the sample is still under water. Any thin or translucent areas are considered to be coated. The Wyoming Highway Department requires that 80% or greater coating be retained in this test.

C. Hot settling test Table 11 Percent Coated Additive Sand Limestone None (control) 0 0 Control+0.5% VR-l Acid" 90 C0ntrol+1.0% VR-i Acid 90 Control+2.0% VR-l Acid 95 The control was a cutback asphalt of the type used in Table 1 Colorado Coating Hot Settling Test Test Wyoming Stripping Additive Test Colorado Coating Lime- (Lander Sand stone Chips) Sediment Sand Limestone Percent Percent Percent Percent Percent Percent Control (None) 0 0 10 0 0 C0ntro1+O.5% A. 80 80 90 Control-H 75 A..- 100 95 100 Control+0.5% B. 100 90 80 Control+1% B... 100 95 100 Control+1% C--- 100 100 95 C0ntro1+2% D 100 100 80 Control+1% E. 100 95 C0ntr0l+2% E. 100 I00 50 C0ntlo1+4% E. 100 100 80 Contro1+l% F. 100 95 40 Control+2% F. 100 100 50 Control+4% F... 100 100 80 Contr0l+2% G-- 100 100 95 Control+2% H 100 100 100 In Table I the various additives employed are identified as follows:

Additive A was the product of Example I. Additive B was the product of Example II. Additive C was the product of Example HI. Additive D was the product of Example IV. Additive E was the product of Example V. Additive F was the product of Example VI. Additives G and H were commercial asphalt additives comprising essentially fatty acid-polyamine amides.

The data in Table I demonstrate the effectiveness of the acid-mixture-arnine reaction product prepared in the manner herein-described, in maintaining asphalt coatings in the both acidic and alkaline mineral aggregates and the heat stability of such products, particularly the polyamine reaction products. The data with respect to the commercial products F and G demonstrate that these products are heat instable and lose their coating ability for both acidic and alkaline mineral aggregates.

The acid mixture-amine reaction products of the present invention can be effectively employed in asphalt compositions for the coating of acidic or alkaline mineral aggregates, such as sand or limestone or mixtures thereof, and for this reason are preferably used. However, there are localities where only alkaline aggregates, such as limestone, are available and therefore asphalt additives which are efiective on only such aggregates can be employed. Under these circumstances the unreacted acid mixture above described can be suitably employed as such in bitumen compositions since it is an effective additive for coating limestone, but not for coating acidic aggregates, such as sand, unless used in excessive amounts based on the asphalt coating material. The eflfectiveness of the acid mixture above is demonstrated by the data in Table II which were obtained by the Modified Colorado Coating Test, above described.

Table I and the VR-l acid is the acid mixture marketed by Rohm and Haas Company (supra).

Similarly, there are localities where only acidic mineral aggregates are available and therefore asphalt additives which are effective on only such aggregates can be successfully employed. Under these circumstances, the unreacted amine residues, such as the Armeen Residues," above described, can be employed as such in bitumen compositions since they are an effective additive for coating acidic aggregates, such as sands, but not for alkaline aggregates. The eifectiveness of the amine residues alone is demonstrated by the data in Table III which were obtained by the modified Colorado coating test, above described, using sand as the aggregate:

Table III Percent sand coated None (control) 0 Control +05% Armeen Residues Control +1.0% Arrneen Residues The control was a cutback asphalt of the type used in Table I and II.

Although the acid mixture-amine reaction products are heat stable at temperatures as high as 230 F., and exhibits essentially no degradation with respect to coating and stripping elficiency, it is advisable to limit the blending and/or storage temperature for the fortified asphalts to temperatures not in excess of about 150 F. and preferably at temperatures not in excess of F. Likewise, asphalts containing the herein-described asphalt additives should preferably be applied at temperatures not to exceed about 230 F.

Percentages expressed herein are volume percentages unless otherwise specified.

While the present invention has been described by reference to specific embodiments thereof, these are given ;by way of illustration only and the invention is not to be limited thereto but includes within its scope such modifications and variations as come within the spirit of the appended claims.

We claim:

1. A bitumen composition comprising a major proportion of bitumen and from about 0.25% to about 5% of an anti-stripping agent selected from the group consisting of (1) a non-volatile residual carboxylic acid mixture having a molecular weight of from about 300 to 1300, obtained as a by-product in the manufacture of sebacic acid by treatment of a member of the group consisting of ricinoleic acid, esters of ricinoleic acid, and salts of the ricinoleic acid with an alkali, and (2) an oilsoluble substantially amido-free reaction product of said non-volatile residual carboxylic acid mixture and a polyamine selected from the group consisting of an alkylene polyamine having from 2 to 8 carbon atoms and an amine of the formula RNH(CH2)3NH2 where R is an alkyl radical having from 10 to 18 carbon atoms, said polyamine and said residual carboxylic acid mixture being reacted in the chemically equivalent ratio of from 1:0.5 to about 1:2 at a temperature of from about 180 F. to about 265 F. for not more than about one hour, and then rapidly reducing the temperature to less than 17 F.

2. A bitumen composition comprising a major proportion of a bitumen and from about 0.25% to about of a residual carboxylic acid mixture having a molecular weight of from about 300 to about 1300, obtained in the manufacture of sebacic acid by treatment of a member of the group consisting of ricinoleic acid, esters of ricinoleic acid and salts of ricinoleic acid with an alkali.

3. A bitumen composition comprising a major proportion of bitumen and from about 0.25 to about 5% of the oil-soluble substantially amide-free reaction product of an alkylene polyamine having 2 to 16 carbon atoms and a non-volatile residual carboxylic acid mixture having a molecular weight of from about 300 to about 1300, obtained as a by-product in the manufacture of sebacic acid by treatment of a member of the group consisting of ricinoleic acid, esters of ricinoleic acid, and salts of ricinoleic acid with an alkali, said polyamine and said residual carboxylic acid mixture being reacted in the chemically equivalent ratio of from about 1:0.5 to 1:2 at a temperature of from about 180 F. to about 265 F., for not more than 1 hour and then rapidly reducing the temperature to less than 170 F.

4. A bitumen composition as described in claim 3 in which the aliphatic polyamine is an alkylene polyamine containing at least two primary amino nitrogen atoms.

5. A bitumen composition as described in claim 3 in which the aliphatic polyamine is an alkylene diamine.

6. A bitumen composition as described in claim 3 in which the aliphatic polyamine is ethylene diamine.

7. A bitumen composition as described in claim 3 in which the aliphatic polyamine is diethylene triamine.

8. A bitumen composition as described in claim 3 in which the aliphatic polyamine is a trialkylene tetramine.

9. A bitumen composition as described in claim 3 in which the aliphatic polyamine is triethylene tetramine.

10. A bitumen composition comprising a major proportion of a bitumen and from about 0.25 to about 5% of the oil-soluble substantially amido-free reaction prodnet of an amine of the formula RNH(CH2)3NHz where R is an alkyl radical having from about 10 to 18 carbon atoms and a non-volatile residual carboxylic acid mixture having a molecular weight of from about 300 to about 1300, obtained as a byproduct in the manufacture of sebacic acid by treatment of a member of the group consisting of ricinoleic acid, esters of ricinoleic acid and salts of ricinoleic acid with an alkali, said polyamine and said residual carboxylic acid mixture being reacted in the chemically equivalent ratio of from about 1:0.5 to 1:2 at a temperature of from about 180 F. to about 265 F., for not more than about 1 hour and then rapidly reducing the temperature to less than F.

11. A roadway construction material resistant to water stripping comprising a mineral aggregate admixed with a coating composition comprising a major proportion of bitumen and from about 0.25 to about 5% of the oilsoluble substantially amido-free reaction product of a polyamine selected from the group consisting of an alkylene polyamine having 2 to 8 carbon atoms and an amine of the formula RNH(CH2) sNHz where R is an alkyl radical having 10 to 18 carbon atoms and a nonvolatile residual carboxylic acid mixture having a molecular weight of from about 300 to about 1300, obtained as a by-product in the manufacture of sebacic acid by treatment of a member of the group consisting of ricinoleic acid, esters of ricinoleic acid and salts of ricinoleic acid with an alkali, said polyamine and said residual carboxylic acid mixture being reacted in the chemically equivalent ratio of from about 1:0.5 to 1:2 at a temperature of from about F. to about 265 F., for not more than about 1 hour and then rapidly reducing the temperature to less than 170 F.

12. The method of forming a water-resistant bond between a mineral aggregate and a bitumen comprising admixing with said bitumen from about 0.25 to about 5% of the oil-soluble substantially amide-free reaction product of a polyamine selected from the group consisting of an alkylene polyamine having 2 to 8 carbon atoms and an amine of the formula RNH(CH2)3NH2 where R is an alkyl radical having 10 to 18 carbon atoms and a non-volatile residual carboxylic acid mixture having a molecular weight of from about 300 to 1300 obtained as a byproduct in the manufacture of sebacic acid by treatment of a member of the group consisting of ricinoleic acid, esters of ricinoleic acid, and salts of ricinoleic acid with an alkali, said polyamine and said residual carboxylic acid mixture being reacted in the chemically equivalent ratio of from about 1:0.5 to about 1:2 at a temperature of from about 180 F. to about 265 F. for not more than about 1 hour and then rapidly reducing the temperature to 170 F., and then applying said mixture of bitumen and said oil-soluble substantially amido-free reaction product to said mineral aggregate.

References Cited in the file of this patent UNITED STATES PATENTS 2,182,056 Bruson Dec. 5, 1939 2,389,680 Mikeska Nov. 27, 1945 2,438,318 Johnson Mar. 23, 1948 2,470,849 Hanson May 24, 1949 2,534,713 Hankin Dec. 19, 1950 

11. A ROADWAY CONSTRUCTION MATERIAL RESISTANT TO WATER STRIPPING COMPRISING A MINERAL AGGREGATE ADMIXED WITH A COATING COMPOSITION COMPRISING A MAJOR PROPORTION OF BITUMEN AND FROM ABOUT 0.25% TO ABOUT 5% OF THE OIL SOLUBLE SUBSTANTIALLY AMIDO-FEE REACTION PRODUCT OF A POLYAMINE SELECTED FROM THE GROUP CONSISTING OF AN ALKYLENE POLYAMINE HAVING 2 TO 8 CARBON ATOMS AND AN AMINE OF THE FORMULA RNH(CH2)3NH2 WHERE R IS AN ALKYL RADICAL HAVING 10 TO 18 CARBON ATOMS AND A NONVOLATILE RESIDUAL CARBOXYLIC ACID MIXTURE HAVING A MOLECULAR WEIGHT OF FROM ABOUT 300 TO ABUT 1300, OBTAINED AS A BY-PRODUCT IN THE MANUFACTURE OF SEBACIC ACID BY TREATMENT OF A MEMBER OF THE GROUP CONSISTING OF RICINOLEIC ACID, ESTERS OF RICINOLEIC ACID AND SALTS OF RICINOLEIC ACID WITH AN ALKALI, SAID POLYAMINE AND SAID RESIDUAL CARBOXYLIC ACID MIXTURE BEING REACTED IN THE CHEMICALLY EQUIVALENT RATIO OF FROM AOUT 1:0.5 TO 1:2 AT A TEMPERATURE OF FROM ABOUT 180* F. TO ABOUT 265* F., FOR NOT MORE THAN ABOUT 1 HOUR AND THEN RAPIDLY REDUCING THE TEMPERATURE TO LESS THAN 170* F. 